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CN102652151B - There is the aldehyde-functionalized polymkeric substance of the stability of enhancing - Google Patents

There is the aldehyde-functionalized polymkeric substance of the stability of enhancing Download PDF

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Publication number
CN102652151B
CN102652151B CN201080056233.3A CN201080056233A CN102652151B CN 102652151 B CN102652151 B CN 102652151B CN 201080056233 A CN201080056233 A CN 201080056233A CN 102652151 B CN102652151 B CN 102652151B
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aldehyde
polymkeric substance
composition
functionalized
reaction
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CN102652151A (en
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海因里克·E·博德
迈克尔·R·圣约翰
刘梅
罗伯特·M·勒韦
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ChampionX LLC
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Ondeo Nalco Co
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

The present invention includes the composition having and be added to the inorganic salt through selecting of aldehyde-functionalized polymeric articles and/or the stability additive of organic salt.Described stability additive can after be added to final polymer product, before causing unfunctionalized functionalization of polymers, add reaction vessel, or add any stage in functionalization process.Invention also discloses for the formation of described composition and use said composition to manufacture the method for cellulosic fibre class medium.

Description

There is the aldehyde-functionalized polymkeric substance of the stability of enhancing
Technical field
The present invention relates in general to the stable formula of aldehyde-functionalized polymkeric substance.More specifically, the present invention relates to the formula of the aldehyde-functionalized polymkeric substance making inorganic salt, organic additive or their combinative stabilities.The present invention be more particularly directed to this stable formula be used in paper industry.
Background technology
Aldehyde-functionalized polymkeric substance based on polyacrylamide (with similar polymkeric substance) provides many benefits manufactured for paper and cardboard, comprises interim wet tenacity, dry strength, wet net intensity, raises the compacting dehydration of gram drying cylinder tackiness agent and increase.Although confirm the benefit of this product well, polymkeric substance is subject to unstable and causes short staging life and low activity concentration close to gelation.Thisly instability limit their uses in some environments, there is the important logical problem of storage and transport, and cause the loss needing batch of material to be processed.In addition, the stability of these polymkeric substance is responsive to activity concentration, and reaches acceptable staging life and need low activity concentration, and this not only adds and manufactures and storage space that the cost but also need of transport increases.
US Pat Appl Ser 10/785,403, " glyoxalated polyacrylamide composition toughener " discloses a kind of polyacrylamide using the acidifying glyoxalated of extra oxalic dialdehyde consumption.US Pat Appl Ser 12/138,766, " polyacrylamide of high solid glyoxalated " discloses a kind of polyacrylamide with the stable glyoxalated of high concentration polymer solid.
Therefore, proved to need to there is the formula with the aldehyde-functionalized polymkeric substance based on polyacrylamide of the stability of improvement and the staging life of prolongation.Due to these reasons, the stability of the prolongation of this polymkeric substance be make us expecting with the staging life at fixing activity concentration time delay long products or in fixing staging life time improve activity concentration.Longer staging life is make us especially expecting in papermaking environments, and this polymkeric substance does not flow continuously in this environment, but only in the grade flowing through selecting.In addition, the staging life of prolongation in the place running into long shipment distance owing to lacking production unit in use but making us expecting.
Summary of the invention
Therefore, the invention provides the novel composition of the aldehyde-functionalized polymkeric substance than prior art formula with the stability of raising.The invention provides novel composition and their preparation method.Being described in of multi-form matrix polymer and preparation method thereof hereafter provides and further in U.S. Patent Application Serial Number 10/764,935, can find in " using aldehyde-functionalized polymkeric substance to improve the method for papermaking machine dewatering ".
In in preferred, the present invention includes the stability additive containing the inorganic salt through selecting be added to about 0.5wt% and the concentration about between 10wt% in polymeric articles and/or organic chemicals composition (this sometimes nominal be " stability additive ").In alternative embodiments, stability additive can after to be added in final polymer product, cause unfunctionalized polymkeric substance functionalized before add reaction vessel, or any stage in functionalization process adds.
In yet another aspect, the present invention is a kind of composition for improving papermaking process.In a preferred embodiment, described composition comprises one or more and has at least about the aldehyde-functionalized polymkeric substance of the weight-average molecular weight of 50,000g/mol and one or more stablizers.
In yet another aspect, the present invention is a kind of method that manufacture has the medium of cellulosic fibre, and the random time being included in the method manufacturing described medium adds above-mentioned disclosed composition to described medium.The preferred aspect of the present invention relates to the manufacture of paper and cardboard in papermaking process.
In a further aspect, the present invention is a kind of method in storage time for extending the composition comprising one or more aldehyde-functionalized polymkeric substance.Described method comprises introduces one or more stablizers to one or more aldehyde-functionalized polymkeric substance, and one or more stablizers wherein said are selected from the group be made up of inorganic salt, organic additive or their arbitrary combination.Measure the storage time relative to the aldehyde-functionalized polymkeric substance of comparable non-stabilization.
Advantage of the present invention is to provide the transportation cost comprising the formula of aldehyde-functionalized polymkeric substance of the reactor productive rate of raising, the storage volume of reduction and/or reduction.
Another advantage of the present invention be extend under fixing activity concentration aldehyde-functionalized polymkeric substance product staging life or improve activity concentration when fixing staging life.
Another advantage of the present invention is to provide the novel method that preparation has the aldehyde-functionalized polymer formulators of the stability of increase.
Other feature and advantage describe at this, and will become obvious from following detailed description, embodiment and accompanying drawing.
Accompanying drawing explanation
Fig. 1 describes the stability of " the during gel number of days " measuring parameter-initial product cloth network gram Field viscosity [BFV] under the polymkeric substance room temperature prepared by the glyoxalated of diallyldimethylammonium chloride-altogether-acrylamide polymer [5/95 mol ratio] when 9wt% for the oxalic dialdehyde-acrylamide mol ratio with 0.8.
Fig. 2 describes the stability of " the during gel number of days " measuring parameter-initial product cloth network gram Field viscosity [BFV] under the polymkeric substance room temperature prepared by the glyoxalated of diallyldimethylammonium chloride-altogether-acrylamide polymer [5/95 mol ratio] when 12wt% for the oxalic dialdehyde-acrylamide mol ratio with 0.8.
Fig. 3 describes the stability of polymkeric substance " the during gel number of days " measuring parameter-initial product cloth network gram Field viscosity [BFV] of 35 DEG C prepared by the glyoxalated of diallyldimethylammonium chloride-altogether-acrylamide polymer [5/95 mol ratio] when 9wt% for the oxalic dialdehyde-acrylamide mol ratio with 0.8.
Fig. 4 describes the stability of polymkeric substance " the during gel number of days " measuring parameter-initial product cloth network gram Field viscosity [BFV] of 35 DEG C prepared by the glyoxalated of diallyldimethylammonium chloride-altogether-acrylamide polymer [5/95 mol ratio] when 12wt% for the oxalic dialdehyde-acrylamide mol ratio with 0.8.
Fig. 5 describe illustrate comprise multiple different additive, use different Adding Way, the stability-enhanced table data of the DADMAC/AcAm formula of 0.8 glyoxalated when there is when room temperature (RT) and 35 DEG C the activity concentration of 9wt%.
Fig. 6 describe illustrate comprise multiple different additive, use different Adding Way, the stability-enhanced table data of the DADMAC/AcAm formula of 0.8 glyoxalated when there is when room temperature (RT) and 35 DEG C the activity concentration of 12wt%.
Fig. 7 described before the reaction of initiation glyoxalated, added and do not add the MgSO of 6wt% 4the present invention 0.8 glyoxalated DADMAC/AcAm formula (as measure pre-reaction) stability test curve (i.e. cloth network gram Field viscosity-number of days).
Embodiment
Be intended to illustrate to give a definition and not intended to be limiting.
" acrylamide monomer " refers to that general formula is
Monomer, wherein R 1for H or C 1-C 4alkyl and R 2for H, C 1-C 4alkyl, aryl or aralkyl.Preferred acrylamide monomer is acrylamide and Methacrylamide.More preferably acrylamide.
" aldehyde " refers to and comprises one or more aldehyde (-CHO) base or can the compound of group of forming reactions aldehyde radical, wherein aldehyde radical can and literary composition in the aldehyde reaction group (such as amino or amide group) of polymkeric substance that describes react.Representational aldehyde comprises formaldehyde, paraformaldehyde, glutaraldehyde, oxalic dialdehyde etc., and arbitrarily other suitable simple function or polyfunctional aldehyde.Preferred oxalic dialdehyde.
" aldehyde-functionalized " refers to the reaction product of precursor polymer and aldehyde, and wherein the aldehyde reaction group of precursor polymer reacts with the terminal carbonyl of aldehyde.
" alkyl " refers to by straight or branched stable hydrocarbon by removing the derivative univalent perssad of single hydrogen atom.Representational alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, hexadecyl etc.
" alkylidene group " refers to by the stable hydrocarbon of straight or branched by removing the derivative divalent group of two hydrogen atoms.Representational alkylidene group comprises methylene radical, ethylidene, propylidene etc.
" amide group " refers to that general formula is-C (O) NHY 1group, wherein Y 1be selected from H, alkyl, aryl and aralkyl.
" amino " refers to that general formula is-NHY 2group, wherein Y 2be selected from H, alkyl, aryl and aralkyl.
" both sexes " refer to by cationic monomer and anionic monomer, and may be the polymkeric substance that other non-ionic monomer derives.Representational amphiphilic polymers comprises the multipolymer be made up of vinylformic acid and DMAEAMCQ, vinylformic acid, the terpolymer etc. be made up of DADMAC and acrylamide.
" aryl " refers to aromatic monocyclic or the polycyclic system of about 6 to about 10 carbon atoms.Aryl is alternatively by one or more C 1to C 20alkyl, alkoxyl group or haloalkyl replace.Representational aryl comprises phenyl or naphthyl, or the naphthyl of the phenyl replaced or replacement.
" aralkyl " refers to aryl-alkylidene group, and wherein aryl and alkylidene group define in the text.Representational aralkyl comprises phenmethyl, styroyl, hydrocinnamyl, 1-naphthyl methyl etc.Preferred phenmethyl.
" the disubstituted ammonium halide monomer of diallyl-N, N-" refers to following general formula (H 2c=CHCH 2) 2n +r 3r 4the monomer of X.Wherein R 3and R 4be C independently 1to C 20alkyl, aryl or aralkyl, and X is anionic counter ion (anionic counterions).Representational anionic counter ion comprises halogen, sulfate radical, nitrate radical, phosphate radical etc.Preferred anionic counter ion is halogenide.Preferred muriate.The disubstituted ammonium halide monomer of preferred diallyl-N, N-is diallyldimethylammonium chloride.
" dispersed polymeres " polymkeric substance refers to the water-soluble polymers be dispersed in the water continuous phase comprising one or more organic salts or inorganic salt and/or one or more waterborne polymerics.The diffuse-aggregate representational embodiment of water-soluble polymers in water continuous phase can at United States Patent (USP) 5, and 605,970,5,837,776,5,985,992,4,929,655,5,006,590,5,597,859 and 5,597,858 and European patent 183,466,657,478 and 630, find in 909.
" emulsion polymer " and " emulsion polymer " refer to be included in aqueous phase according to aldehyde-functionalized polymkeric substance of the present invention, for the hydrocarbon ils of oil phase and the polymer emulsions of water-in-oil emulsifier.Inverse emulsion polymer is that hydrocarbon and water-soluble polymers are dispersed in alkyl body continuously.Then, shear by using, dilution and usual another kind of tensio-active agent release polymers and " conversions " or activate inverse emulsion polymer with use from particle.See the United States Patent (USP) 3,734,873 be incorporated herein by reference.The representativeness of high molecular weight inverse emulsion polymer is prepared in United States Patent (USP) 2,982, and 749,3,284,393 and 3,734, describe in 873.Also can see Hunkeler etc. " mechanism, dynamic property and model that anti-phase micro-suspension of acrylamide is all polymerized; " polymkeric substance, volume 30 (1), 127-42 page (1989) and Hunkeler etc. " mechanism of homogeneous nucleation, dynamic property and model: the 2. copolymerization of acrylamide and quaternary ammonium; " polymkeric substance, volume 32 (14), 2626-40 page (1991).
" monomer " refers to polymerisable allylic cpd, vinyl compound or acrylic compound.Monomer can be negatively charged ion, cationic, non-ionic or zwitterionic.Preferred vinyl monomer, and more preferably Acrylic Acid Monomer.
Representational nonionic, water-soluble monomer comprise acrylamide, Methacrylamide, N, N-DMAA, N, N-acrylamide, NIPA, N-vinyl formamide, N-vinyl methylacetamide, N-vinyl four chlorination pyrroles, HEMA, hydroxyethylmethacry,ate, acrylate, hydroxy propyl methacrylate, N tert butyl acrylamide, N hydroxymethyl acrylamide, vinyl-acetic ester, vinyl alcohol etc.
Representational anionic monomer comprises vinylformic acid and salt thereof, and this vinylformic acid and salt thereof include but not limited to sodium acrylate and ammonium acrylate; Methacrylic acid and salt thereof, this methacrylic acid and salt thereof include but not limited to sodium methacrylate and ammonium methacrylate; 2-acrylamide-2-methyl propane sulfonic (AMPS); The sodium salt of AMPS; Sodium vinyl sulfonate; Styrene sulfonate; Toxilic acid and salt thereof include but not limited to other water-soluble form of sodium salt and ammonium salt, sulfonate, methylene-succinic acid, sulfopropyl acrylate or methacrylic ester or these or other polymerisable carboxylic acid or sulfonic acid.Sulfomethylated acrylamide, allylsulfonate, sodium vinyl sulfonate, methylene-succinic acid, propyl amides methylbutyric, fumaric acid, vinyl phosphonate, vinyl sulfonic acid, allyl phosphonic acid, sulfomethylated acrylamide, phosphonomethylated acrylamide, itaconic anhydride etc.
Representational cationic monomer comprises monoallyl amine, diallyl amine, vinyl-amine, dialkyl aminoalkyl acrylates and methacrylic ester and their quaternary salt or hydrochlorate include but not limited to dimethylamino vinyl acrylate methyl chloride quaternary salt (DMAEAMCQ), dimethyl amino ethyl acrylate methyl sulfate quaternary salt, dimethyl amino ethyl acrylate toluene(mono)chloride quaternary salt, dimethyl amino ethyl acrylate vitriol, dimethyl amino ethyl acrylate hydrogen chlorate, dimethyl amino ethyl methacrylate methyl chloride quaternary salt, dimethyl amino ethyl methacrylate methyl sulfate quaternary salt, dimethyl amino ethyl methacrylate toluene(mono)chloride quaternary salt, dimethyl amino ethyl methacrylate vitriol, dimethyl amino ethyl methacrylate hydrogen chlorate, dialkylaminoalkyl acrylamide or Methacrylamide and their quaternary salt or hydrochlorate such as acrylamidopropyl trimethyl ammonium chloride, dimethylaminopropylacryl amido sulfuric acid methyl esters quaternary salt, dimethylaminopropylacryl amido sulfuric acid salt, dimethylaminopropylacryl acylamino hydrogen oxymuriate, methacryiamidopropyl trimethyl ammonium chloride, dimethylaminopropyl Methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfate, dimethylaminopropyl methacrylamide hydrochloride salt, diethylamino ethyl propylene acid esters, diethylamino ethylmethyl acrylate, diallyidiethylammonium ammonium chloride and diallyldimethylammonium chloride (DADMAC).Alkyl is generally C 1to C 4alkyl.
Representational zwitterionic monomer is comprise the positively charged ion of equal proportion and the polymerizable molecules of negatively charged ion (charged) functionality, so that molecule is overall neutral substantially.Concrete representational zwitterionic monomer comprises N, N-dimethyl-N-acryl oxygen ethyl-N-(3-sulfopropyl)-ammonium trimethyl-glycine, N, N-dimethyl-N acrylamide base propyl group-N-(2-carboxymethyl group)-ammonium trimethyl-glycine, N, N-dimethyl-N acrylamide base propyl group-N-(3-sulfopropyl)-ammonium trimethyl-glycine, N, N-dimethyl-N acrylamide base propyl group-N-(2-carboxymethyl group)-ammonium trimethyl-glycine, 2-(methylthio group) ethyl-methyl acryl-S-(sulfopropyl)-sulfonium trimethyl-glycine, 2-[(2-acryloyl ethyl) dimethyl amine] ethyl 2-phosphonomethyl ester, 2-(acryl oxygen ethyl)-2 '-(trimethyl ammonium) ethyl phosphonate, [(2-acryloyl ethyl) dimethyl amine] methyl-phosphorous acid, 2-methyacryloxyethyl phosphorylcholine (MPC), 2-[(3 acrylic acid aminocarbonyl propyl) dimethyl amine] ethyl 2 '-sec.-propyl phosphonic acid ester (AAPI), l-vinyl-3-(3-sulfopropyl) imidazolium hydroxide, (2-acryloyl ethyl) carboxymethylmethyl sulfonium muriate, l-(3-sulfopropyl)-2-vinyl pyridine trimethyl-glycine, N-(4-sulphur butyl)-N-methyl-N, N-diallyl amine ammonium trimethyl-glycine (MDABS), N, N-diallyl-N-methyl-N-(2-sulfoethyl) ammonium trimethyl-glycine etc.
" papermaking process " means the method by pulp manufacture paper and board product, comprising: form aqueous fiber element paper making raw material (alternatively, together with mineral filler, as calcium carbonate, clay etc.), makes this raw material draining to form thin slice and this thin slice dry.Be understood that the raw material that can use and be applicable to arbitrarily.Representational raw material comprises, the arbitrary combination of the plastic optical fibre of such as new paper pulp, recycled pulps, kraft pulp (bleaching with unbleached), sulfite pulp, mechanical pulp, polymerization etc. and above paper pulp.Form paper making raw material, the step of draining and drying can well known to a person skilled in the art that any means is carried out.Other additive for paper making can be utilized as the additive of polymer treatment of the present invention, but it must be emphasized that and do not need additive for effective activity.This additive for paper making comprises, such as retention aid (such as particulate, flocculation agent, polymerization and inorganic coagulant etc.), wet tenacity and dry strength additive (such as cationic starch, daiamid epoxy chloropropane base polymer), sizing agent (such as rosin size, alkylene vinyl ketone dimer, alkenyl succinic anhydride) etc. and above combination.
The aldehyde-functionalized polymkeric substance of the present invention can be added in the wet end position for wet end additive, is such as added in thin stock or thick stock.Actual wet end position is not thought crucial, but aldehyde-functionalized polymkeric substance preferably adds before other cationic additive adds.It is optional that they are added to wet end, selects after paper is formed (such as close to pressing part) to add them and also can implement.Such as, polymkeric substance can be injected in wet online before entering pressing part, and this is that the optimal way of interpolation is to reduce consumption or to reduce the interference effect that may appear at wet end place.Other traditional wet end additive can use with aldehyde-functionalized combination of polymers, comprises retention aid, strength additive as starch, sizing agent etc.Although aldehyde-functionalized polymkeric substance has the sizable validity proved in the application of paper and cardboard, the stability of these polymkeric substance put into practice by the present invention thinks that be useful in the application using arbitrarily this polymkeric substance, and does not need to be limited to papermaking.
Such as, when using the aldehyde-functionalized polymkeric substance as described herein with clean anionic charge, method polymkeric substance being fixed to fiber is needed.This fixing usually by using cationic materials to realize together with polymkeric substance.This cationic materials is the most often condensing agent, or for inorganic (such as alum, poly aluminium chloride, iron(ic) chloride or ferric sulfate and arbitrarily other positively charged ion hydrolysis salt) or organically (polymkeric substance being low to moderate intermediate molecular weight of the PEI of such as p-DADMAC, EPI/DMA, PEI, modification or arbitrarily other high charge density).In addition, the cationic materials such as starch, wet strength additives or the reservation additive that add for other object also can be used for fixing anionic polymer.Do not need extra additive polymkeric substance aldehyde-functionalized for positively charged ion to be fixed to material composition (such as fiber and filler).
In one embodiment, depend on concrete papermaking environments (paper making equipment of use and papermaking starting material) and desired active species, useful raising in dehydration can use the aldehyde-functionalized polymer loading in the dry fiberoptic scope of 0.05 to 15.0lb polymkeric substance/ton and realize, and usually in the scope of 0.5 to 6.0lb/ ton, realizes economic useful result.Be understood that desired aldehyde-functionalized polymkeric substance is for the gradational paper of institute and cardboard, it is useful for comprising plate level, fine papers level and fabric/towel level.Use and be with or without the OCC(old corrugated container of mixing waste) recirculation plate level, alkaline fine paper level and fabric/towel level respond especially.
The polymkeric substance comprised in composition of the present invention and method are aldehyde-functionalized polymkeric substance prepared by precursor polymer by comprising one or more aldehyde reaction parts or preformed polymkeric substance and one or more aldehyde reactions.This polymkeric substance can have that various structures comprises linearly, side chain, star-like, block, grafting, tree-shaped etc., and other suitable structure arbitrarily.Preferred polymkeric substance comprises and has amino or the amide group polymkeric substance as aldehyde reaction part.These precursor polymers or preformed polymkeric substance can be derived by the source of any appropriate and use the method for any appropriate to synthesize.Such as, aldehyde reaction polymkeric substance is formed by emulsion, dispersion or solution polymerization and can comprise and has the non-ionic, cationic, negatively charged ion of polymkeric substance and zwitterionic monomer kind.And these monomer kinds can exist with any amount and arbitrary combination in polymkeric substance.
In one embodiment, polyamine is by preformed polyamide modified obtained, and such as, as United States Patent (USP) 6,610,209 and 6,426, the 383 use acid described or alkali are prepared by the hydrolysis of acrylamide-vinyl formamide copolymers.
In one embodiment, as United States Patent (USP) 4, the amido exchange interaction (transamidation) of 919, the 821 direct amidations by poly-alkyl carboxylic acid described and the multipolymer that comprises carboxylic acid and (methyl) acrylamide unit prepares polyaminoamide.
In another embodiment, preformed polymkeric substance can be prepared as emulsion polymer or emulsion polymer.Such as, aqueous phase by mixing one or more water-soluble monomers and any polymeric additive as inorganic salt, sequestrant, pH buffer reagent etc. and prepare in water.Oil phase is prepared by inert hydrocarbon liquids and one or more oil soluble surfactants being mixed.Surfactant mixture should have low hydrophile-lipophile balance value (HLB), to guarantee the formation of water-in-oil emulsion.The commercially available suitable tensio-active agent editor for water-in-oil emulsion polymerization is in the North America version of McCutcheon ' s Emulsifiers & Detergents.Heating oil phase can be needed to guarantee the formation of even oil solution.Then, oil phase loading is furnished with in the reactor of mixing tank, thermopair, nitrogen purge tube and condenser.Be added to along with strong stirring aqueous phase in the reactor comprising oil phase to form emulsion.
The emulsion of gained is heated to desired temperature, by purging with nitrogen gas, then adds radical initiator.The stirred reaction mixture several hours when desired temperature in a nitrogen atmosphere.When reaction completes, water-in-oil emulsion polymer is cooled to room temperature, wherein can adds post polymerization additive desired arbitrarily, as antioxidant or high HLB tensio-active agent (as United States Patent (USP) 3,734,873 is described).Gained emulsion polymer is free-pouring liquid.By adding in water by the emulsion polymer of desired amount, under the existence having high HLB tensio-active agent, strong stirring can generate the aqueous solution (as United States Patent (USP) 3,734, described in 873) of water-in-oil emulsion polymer.
In another embodiment, preformed polymkeric substance used in this invention can be dispersed polymeres.For the preparation of in the ordinary method of dispersed polymeres, comprise one or more inorganic or organic salts, the aqueous solution of one or more water-soluble monomers, arbitrarily polymeric additive such as processing aid, sequestrant, pH buffer reagent and water soluble stabilizer polymkeric substance loads and be furnished with in the reactor of mixing tank, thermopair, nitrogen purge tube and water condenser.This monomer solution of strong stirring, and be heated to the temperature of expectation, then add radical initiator.This solution uses nitrogen to carry out purge, keeps temperature simultaneously and mixes several hours.After current, mixture be cooled to room temperature, and in reactor, load any post polymerization additive.The water of water-soluble polymers is separated into product viscosity continuously and is generally the pourable liquid within the scope of about 100 to about 10,000cP measured when low-shearing power.
In another embodiment, preformed polymkeric substance used in this invention or precursor polymer are solution polymer.For the preparation of in the ordinary method of solution polymer, preparation comprises one or more water-soluble monomers and polymeric additive other arbitrarily as the aqueous solution of sequestrant, pH buffer reagent etc.This mixture loads to be furnished with in the reactor of mixing tank, thermopair, nitrogen purge tube and water condenser.This solution of powerful mixing, is heated to temperature required, then adds one or more radical polymerization initiators.This solution uses nitrogen to carry out purge, keeps temperature simultaneously and mixes several hours.Usually, the viscosity of solution increases during this period.After completion of polymerization, reactor content is cooled to room temperature then to shift to preserve.The viscosity B coefficent of solution polymer is very large, and depends on the concentration of active polymer composition, molecular weight and structure.
Polyreaction is caused by the method causing suitable free radical to produce arbitrarily usually.The free radical that preferred heat is derivative, wherein free radical kind is by heat, and the homolysis of azo, superoxide, hydroperoxide and perester compound is dissociated generation.Preferred initiator is for comprising 2, two (2-amidine propane) dihydrochloride, 2 of 2 '-azo, two [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, 2 of 2 '-azo, two (isopropyl cyanide) (AIBN), 2 of 2 '-azo, the azo-compound of 2 '-azo two (2,4-methyl pentane nitrile) (AIV) etc. and their combination.Preferred initiator comprises superoxide, as ammonium persulphate, Sodium Persulfate etc., and their combination.
In alternate embodiments, polymerization process can carry out in a batch process or with multiple step.In representational batch process, all monomers one react, and in the method for fractional steps or semi-batch process, a part of monomer separates and adds to affect the composition drift of multipolymer or the formation of discrete particles in time from principal reaction.In the embodiment of continuation method, all monomers add in time and differently affect the change of composition.
Can selective polymerization and/or post-polymerization condition, make the resulting polymers (i.e. preformed polymkeric substance or precursor polymer) comprising aldehyde reaction part have molecular weight at least about 1,000g/mol, preferably about 2,000 to about 10,000,000g/mol.Then this polymkeric substance is by functionalized with one or more aldehyde reactions.Suitable aldehyde comprises containing one or more aldehyde (-CHO) functional group (i.e. simple function or multifunctional aldehyde) and has the reactive any compound being enough to react with the aldehyde reaction part of polymkeric substance (such as amino or amide group).Representational aldehyde comprises formaldehyde, paraformaldehyde, glutaraldehyde, oxalic dialdehyde etc., and other suitable reactive aldehyde any.
In one embodiment, aldehyde-functionalized polymkeric substance is prepared by reaction under polymeric amide or polyamine and the pH of one or more aldehyde between 4 to 12.Polymer backbone (namely having preformed polymkeric substance or the precursor polymer of aldehyde reaction part) adds that the total concn of aldehyde is between about 2 to about 35 weight percents.Usually, in order to the product stability that better speed of reaction controls and improves, the aqueous solution of polymer backbone is prepared.The pH of waterborne polymeric skeleton solution increases to about 4 to about between 12.Temperature of reaction is generally about 20 DEG C to about 80 DEG C, preferably about 20 DEG C to about 40 DEG C.This water-based aldehyde solution is added to waterborne polymeric skeleton solution, and well blend is to prevent gel formation simultaneously.After crosslinking reaction, the speed increased by Brookfield viscometer monitoring viscosity.The enhancing that the increase of the viscosity increase expression polymericular weight of 0.5cps and polymer precursor are cross-linked.
Usually, desired viscosity increases corresponding to desired active rank, and this activity reaches the point of maximum value or decay of activity usually at specific viscosity place.Speed of reaction depends on ratio and the pH of the total concn of temperature, polymkeric substance and aldehyde, aldehyde and acid amides/amine functional group.When the ratio of the total concn of temperature, polymkeric substance and aldehyde, aldehyde and acid amides/amine functional group or pH increase, glyoxalated (oxalic dialdehyde is used as aldehyde in this case) of higher rate expects.The speed of reaction is by reducing the ratio of the total concn of polymkeric substance and aldehyde, temperature, aldehyde and acid amides/amine functional group or pH(to about 2 to about between 3.5) and slow down.At the end of reaction unreacted aldehyde amount along with the ratio of aldehyde and acid amides/amine functional group increase and increase.
In a preferred embodiment, precursor polymer is prepared by DADMAC and acrylamide copolymer.Monomer, DADMAC and acrylamide exist with the weight ratio of about 5/95 to about 95/5 respectively in precursor polymer.This front precursor copolymer preferably have about 17,000g/mol weight-average molecular weight and and such as glyoxal reaction.Oxalic dialdehyde amount can change but usually be added to the oxalic dialdehyde-acrylamide mol ratio reaching 0.1 to 1.0.The weight ratio of preferred DADMAC/ acrylamide is 10/90.
Preferred reaction conditions makes the mol ratio of polymer precursor and aldehyde be about 0.05 to about 1.5.The mol ratio of this scope can cause the aldehyde reaction part of many precursor polymers to functionalised.Such as, about 9 molar percentages can functionalised to the aldehyde reaction part being greater than 50 molar percentages.And depend on the concrete combination of the aldehyde of selection, the part of having reacted of about 20 to about 50 per-cents or more can be multicomponent reaction.
In one embodiment, 15 molar percentages in polymkeric substance, preferably at least about the amino of 20 molar percentages or amide group and aldehyde reaction to form aldehyde-functionalized polymkeric substance.The aldehyde-functionalized polymkeric substance of gained has the weight-average molecular weight at least about 100,000g/mol, is preferably at least about 300,000g/mol.
In one embodiment, the precursor polymer that aldehyde-functionalized polymkeric substance has the aldehyde reaction part of the arbitrary combination being selected from amine, acid amides and hydroxyl by one or more is formed.
In another embodiment, aldehyde-functionalized polymkeric substance is comprise the acrylamide monomer of about 1 to about 99 molar percentage and the about 95 molar percentages multipolymer to one or more positively charged ions of about 1 molar percentage, negatively charged ion, nonionic or zwitterionic monomer or their mixture.The multipolymer obtained by nonionic aldehyde reaction monomer and cationic monomer preferably has the cationic charge of about 1 to about 50 molar percentage, more preferably from about 1 to about 30 molar percentage.The multipolymer obtained by nonionic aldehyde reaction monomer and anionic monomer preferably has the anionic charge of about 1 to about 50 molar percentage, more preferably from about 1 to about 30 molar percentage.Amphoteric ion polymer preferably includes 1 to about 95 molar percentage, preferably the zwitterionic monomer of 1 to about 50 molar percentage.
In another embodiment, aldehyde-functionalized polymkeric substance is the amphiphilic polymers preferably with overall positive charge.Preferred amphiphilic polymers is made up of with the residual monomer being preferably aldehyde reaction monomer the cationic monomer of about 40 molar percentages at the most and the anionic monomer of about 20 molar percentages at the most.Preferred amphiphilic polymers comprises the cationic monomer of about 5 to about 10 molar percentages and the anionic monomer of about 0.5 to about 4 molar percentage and is preferably the residual monomer of aldehyde reaction monomer.
In one embodiment, disclosed polymer composition comprises the unreacted aldehyde of about 10 to about 90 molar percentages.
In another embodiment, product storage stability depends on the total concn of the total amount of the temperature of storage, initial product viscosity, reactive monomer, polymkeric substance and aldehyde, the ratio of aldehyde and aldehyde reaction functional group, precursor molecular-weight average and pH.Usually, the pH of product remains on low pH(2 to 3.5) and the total concn of aggregation thing and aldehyde to strengthen storage stability.
In the preferred embodiment of the present invention, based on the gross weight of said composition, aldehyde-functionalized polymer composition of the present invention comprises the stablizer of the amount within the scope of about 0.5wt% to about 10wt% further.
Adding one or more stablizers to composition causes storage time or staging life to extend.In the preferred method in the storage time for extending more how aldehyde-functionalized polymer composition of the present invention, one or more stablizers are incorporated in reaction mixture when precursor carries out aldehyde-functionalized, or are incorporated in aldehyde-functionalized product.The stablizer added preferably extended relative to the storage time measured by the aldehyde-functionalized polymkeric substance of comparable non-stabilization.Exemplary process for measurement stability comprises the viscosity measuring product, until it is increased to the time demonstrating gel during the storage time of the aldehyde-functionalized polymers lengthen relative to comparable non-stabilization fast.The example of this measuring technology is provided in following embodiment 8.
In one embodiment, the method in this prolongation storage time can comprise the following steps: (i) pre-formed polymkeric substance with one or more aldehyde reaction parts, (ii) one or more reactive aldehyde is added to preformed polymkeric substance, (iii) reaction between preformed polymkeric substance and one or more reactive aldehyde is caused to form one or more aldehyde-functionalized polymkeric substance, (iv) at any time with arbitrary velocity before above step, period or afterwards progressively, in batches, semi-batch, add one or more stablizers continuously or off and on.
In another embodiment, this method can comprise (i) pre-formed polymkeric substance with one or more aldehyde reaction parts, (ii) one or more reactive aldehyde are added with forming reactions mixture to preformed polymkeric substance, (iii) add one or more stablizers to this reaction mixture, and (iv) causes reaction between preformed polymkeric substance and one or more reactive aldehyde to form stable aldehyde-functionalized polymer composition.
In another embodiment, this method can comprise (i) pre-formed polymkeric substance with one or more aldehyde reaction parts, (ii) one or more reactive aldehyde is added to preformed polymkeric substance, (iii) cause reaction between preformed polymkeric substance and one or more reactive aldehyde to form one or more aldehyde-functionalized polymkeric substance, and (iv) adds one or more stablizers to form stable aldehyde-functionalized polymer composition to aldehyde-functionalized polymkeric substance.
Representational stablizer is inorganic salt, organic additive and their combination.
The representative classes of inorganic salt comprises an alkali metal salt, alkaline earth salt, transition metal salt, their hydrate etc., and the arbitrary combination of above component.The specific examples of inorganic salt comprises MgSO 4with its hydrated form (such as MgSO 47H 2o), MgCl 2with its hydrated form (such as MgCl 26H 2o), magnesium acetate and its hydrated form (such as Mg (OAc) 24H 2o), ZnSO 4with its hydrated form (such as ZnSO 47H 2o), Na 2sO 4, NaCl, (NH 4) 2sO 4, and the arbitrary combination of above component.
Organic additive is selected from glycols, three alcohols, polyalcohols, carbohydrate etc. usually, and the arbitrary combination of above component.The specific examples of organic additive comprises glycerol, ethylene glycol, urea, and the arbitrary combination of above component.
Can understand above better by reference to following embodiment, these embodiments be intended to the object of explanation but not limit the scope of the invention.
Embodiment 1
The initial initial viscosity of product refers to cloth network gram Field viscosity [BFV], measures when this viscosity place acid stops aldehyde-functionalized (glyoxalated in this specific embodiment) crosslinking reaction and uses No. 1 cloth network gram Field rotor at 60rpm and 25 DEG C.In order to make suitably comparing of stability between two samples, these samples should have identical initial BFV.In fact, the sample manufacturing identical initial BFV is difficult to realize, because viscosity controller is limited.
Therefore, two kinds of active concentrations are measured when room temperature (21 DEG C) and 35 DEG C containing the stability of the sample of additive in the scope of initial BFV.Use the beta stability line of number of days-initial BFV measurement during gel, by this data determination quadratic polynomial, then this equation is for determining the stability under any initial BFV.Fig. 1 to 4 is provided for determining that the curve of untreated samples stability and polynomial expression are determined, this untreated sample is for comparing the stability of the sample comprising different additive.These data also illustrate that the significantly change of the stability of the function as initial BFV.
Embodiment 2
Fig. 5 and 6 describes the comparison between the stability of the sample using suitable temperature and wt% polymer actives to be prepared by different additives and addition means and the reference stability calculated by the equation shown in Fig. 1 to 4.The multiple additives that in Fig. 5 and 6, the detection of table showed to add after testing can realize significantly improving of stability.Particularly, MgSO 47H 2o, MgCl 26H 2o, ZnSO 47H 2o, glycerol and ethylene glycol are shown to be the useful additive of the stability for improving aldehyde-functionalized polymkeric substance.Add MgSO 47H 2the pre-glyoxalated of O shows the maximum raising providing stability.
Embodiment 3
This example illustrates the preparation of 95/5mol% acrylamide/DADMAC multipolymer.To being furnished with 1 of mechanical stirrer, thermopair, condenser, nitrogen purge tube and charging opening, 500-mL reaction flask add the deionized water of 116.4g or soft water, the phosphoric acid of 26.3g, 62% of 63.8g the aqueous solution of diallyldimethylammonium chloride (obtain from Ondeo Nalco Co., Naperville, IL), the sodium formiate of 7.6g and the tetrasodium salt of EDTA of 0.09g.This reaction mixture stirs with 400rpm and uses the water-based 50% sodium hydroxide solution adjustment pH to 4.7 of 17.3g to 4.9.Gained mixture is heated to 100 DEG C and uses nitrogen with 50mL/min purge.When reaching 100 DEG C, within the time of 135 minutes, add the ammonium persulfate aqueous solution of 25.0% of 17.6g to this reaction mixture.After ammonium persulphate starts to add five minutes, within the time of 120 minutes, add the acrylamide solution of 49.5% of 750.9g to this reaction mixture.After ammonium persulphate adds, this reaction keeps 180 minutes at 100 DEG C.Then this reaction mixture be cooled to envrionment temperature and use 50% aqueous sodium hydroxide solution or vitriol oil adjustment pH to 5.2 to 5.8.This product be viscosity, yellow solution that can be bright.This product has the molecular weight of about 20,000g/mol.
Embodiment 4
This embodiment illustrates the glyoxalated of the acrylamide/DADMAC multipolymer of the 95/5mole% of oxalic dialdehyde-acrylamide mol ratio when 9.0% actives (total oxalic dialdehyde and polymkeric substance) of use 0.8 to 1.To be furnished with mechanical stirrer, thermopair, condenser, charging opening and be positioned at reactor bottom sampling valve 2,000-mL reaction flasks in add the acrylamide/DADMAC aqueous copolymers solution of 95/5mole% as preparation in embodiment 4 and the deionized water of 1304.0g or the soft water of 41% of 238.0g.This polymers soln is stirred with 400rpm.The pH to 8.8 of this solution is adjusted to 9.1 by 50% aqueous sodium hydroxide solution adding 5.8g.This temperature of reaction is set in 24 to 26 DEG C.Oxalic dialdehyde (40% aqueous solution of 143.0g) is added to this reaction mixture within the time of 20 to 30 minutes.Cloth network gram Field viscosity (the Brookfield Programmable LVDV-II+ viscometer of this reaction mixture after oxalic dialdehyde adds, LV No. 1 rotor is when 60rpm, Brookfield Engineering Laboratories company limited, Middleboro, MA) be about 4 to 5cps.Within the time of 20 to 30 minutes, add 10% aqueous sodium hydroxide (25g) adjust the pH to 7.5 of this reaction mixture to 8.8.Cloth network gram Field viscosity (the BrookfieldProgrammable LVDV-II+ viscometer of this reaction mixture after sodium hydroxide adds, LV No. 1 rotor is when 60rpm, Brookfield EngineeringLaboratories company limited, Middleboro, MA) be about 4 to 5cps.Along with the pH of good this reaction mixture of stirring is maintained at about 7.0 to 8.8 about 24 to 26 DEG C time.Monitor this cloth network gram Field viscosity and be more than or equal to 1cps (5 to 200cps reaching desired viscosity increase, >100, time 000g/mol), be reduced to 2 to 3.5 fully to reduce speed of reaction by the pH adding sulfuric acid (93%) this reaction mixture.Find that the speed that viscosity increases depends on reaction pH and temperature.More the speed that increases of high viscosity is faster for the pH of reaction mixture.The speed of viscosity increase is controlled by the pH reducing reaction mixture.This product is bright muddy body, colourless to the fluid faint yellow, cloth network gram Field viscosity is more than or equal to 5cps.When the cloth network gram Field viscosity of product is less than 40cps and when making to be diluted with water to lower Percent Active thing when product, products obtained therefrom is more stable when storing.This product is prepared with the gross activity thing of higher or lower per-cent by adjusting desired targeted product viscosity.The C of the sample of preparation 13nMR analyzes the display oxalic dialdehyde unreacted of about 70 to 80% and the acrylamide unit of 15 to 35 molar percentages and glyoxal reaction.
Embodiment 5
This example illustrates the oxalic dialdehyde-acrylamide mol ratio of use 0.8 to 1 at 9.0% actives (total oxalic dialdehyde and polymkeric substance) and the MgSO adding 6wt% 47H 2the glyoxalated of the acrylamide/DADMAC multipolymer of 95/5mole% during O forms stable product.To be furnished with mechanical stirrer, thermopair, condenser, charging opening and be positioned at reactor bottom sampling valve 2,000-mL reaction flasks in add 41% of 283.2g as embodiment 3 prepare the acrylamide/DADMAC aqueous copolymers solution of 95/5mole%, the MgSO of 123g 47H 2the deionized water of O and Isosorbide-5-Nitrae 35.0g or soft water.This polymers soln is stirred with 500rpm.By add 12g 50% aqueous sodium hydroxide solution adjust the pH to 8.8 of this solution to 9.1.This temperature of reaction is set in 24 to 26 DEG C.Oxalic dialdehyde (40% aqueous solution of 170.0g) is added to this reaction mixture within the time of 30 to 40 minutes.After oxalic dialdehyde adds, the cloth network gram Field viscosity (BrookfieldDV-E viscometer No. 1 rotor is when 60rpm) of this reaction mixture is about 5 to 6cps.10% aqueous sodium hydroxide (11.5g) is used to adjust the pH to 7.5 of this reaction mixture to 8.8.After sodium hydroxide adds, the cloth network gram Field viscosity (Brookfield DV-E viscometer No. 1 rotor is when 60rpm) of this reaction mixture is about 5 to 6cps.Along with the pH of good this reaction mixture of stirring is maintained at about 7.0 to 8.8 about 24 to 26 DEG C time.Monitor cloth network gram Field viscosity and when reaching target viscosities value (5 to 200cps, >100,000g/mol), be reduced to 2 to 3.5 by the pH adding sulfuric acid (93%) this reaction mixture.This product is bright muddy body, colourless to the fluid faint yellow, cloth network gram Field viscosity is more than or equal to 6cps.This product is prepared with the gross activity thing of higher or lower per-cent by adjusting desired targeted product viscosity.Also wt% that can be desired arbitrarily before glyoxalated, period or add stablizer afterwards.
Embodiment 6
This embodiment illustrates by MgSO 47H 2the existence of O stability additive does not reduce the compacting dehydrating effect of representative aldehyde-functionalized polymkeric substance.The DADMAC/ acrylamide polymer of the glyoxalated evaluated uses the oxalic dialdehyde-acrylamide mol ratio of 0.8 to prepare when the activity concentration of 9.0wt%.Polymkeric substance uses and does not use MgSO 47H 2o is prepared when 6.0wt% concentration and is compared by Paper Machine Trial.
This test on having, net former and the fourdrinier machine of pressing part that is made up of two simple roller stone press is carried out, and first in two simple roller stone press has vacuum furnace.Compacting dehydration test is at 119#/3000ft 2paper weight and 16wt% greyness of paper alkaline fine paper on carry out.Dewatered by vapor pressure monitoring compacting in major portion drying machine before size compacting.By changing to the amount adjustment paper humidity of drying machine some vapor to the steady state value as represented by vapour pressure.If paper humidity increases, need larger vapor pressure or reduce machine speed.Once reach maximum vapor pressure, machine normally must be decelerated to and keep constant paper humidity.Maximum vapour pressure on this machine is 95psi.Usually, pressure lower is a little adopted so that some in keeping system are lax to process the natural trend appeared on all paper machines.
Test-results is shown in table 1.Test never contains the MgSO of 6wt% with the actives consumption that the shredder of this rank normally uses 47H 2the product of O stablizer starts, and is fed to thick stock.Gather the baseline data of machine speed and major portion steam.Then, identical actives basis is used the MgSO containing 6wt% 47H 2the product of O stablizer replaces not containing the product of stablizer.After one period of equilibration time, stablize that machine speed does not change and vapour pressure reduces a little.Thus less steam can be used to keep machine speed, show improvement a little possible in compacting dehydration.Then, product consumption is reduced to zero (being expressed as "None" in table 1).If this point illustrates removing product what may occur.And for example table 1 records, and after one period of equilibration time, machine speed is reduced to 1,067ft/min from 1,122ft/min but needs vapor pressure higher a little to reach this slower speed.This data presentation works as the MgSO of the 6wt% being used for static stabilization 47H 2the loss suppressing dehydration activity is there is not when O is present in product.
table 1: time shaft and result
Length (min) Product Actives consumption Machine speed Major portion steam
120 Not containing the MgSO of 6wt% 4·7H 2O 2#/ton 1122 91psi
126 MgSO containing 6wt% 4·7H 2O 2#/ton 1122 89psi
72 Nothing Without (OFF) 1067 92psi
Embodiment 7
This example illustrates the wet tenacity effect of representative aldehyde-functionalized polymkeric substance and dry strength effect not because of stablizer and damage.DADMAC/ acrylamide [10/90 weight ratio] polymkeric substance of evaluated glyoxalated by mol ratio be 0.8 oxalic dialdehyde-acrylamide mol ratio prepare when the activity concentration of 9.0wt%.Polymkeric substance uses and does not use MgSO 47H 2o is prepared when the concentration of 6.0wt% and the evaluation of room handsheet compares by experiment.Handsheet uses the Noble & Wood handsheet forming device with single roll gap press and rotating dryer to make by unrefined bleached softwood kraft fiber.Paper weight (basis weight) is for 60gsm and raw material pH is 6.3.This paper is processed in controlled temperature and humidity indoor [23 DEG C and 50% humidity] and spends the night, and carry out physical test at identical conditions.Thwing-Albert universal testing machine and 4 inch span are used to measure baked tensile strength according to TAPPI method T494.Stretching paper weight corrects, and result is expressed as tensile figure.Substantially determine that green tensile strength makes the center of test strip saturated except test strip contacts 1/4 inch of wet painting brush with deionized water by the method identical with baked tensile strength.
Present containing with following table 2 or do not contain the MgSO of 6wt% 47H 2the baked tensile strength exponential sum green tensile strength index of the DADMAC/AcAm polymkeric substance of the equal glyoxalated of O stability additive.These results illustrate that adding fashionable discovery strength property at additive does not lose.
table 2: tensile figure result
Embodiment 8
Fig. 7 provides before the reaction of initiation glyoxalated, adds and do not add the MgSO of 6wt% 4the explanation of stability test curve (namely cloth network gram Field viscosity is to number of days) of DADMAC/AcAm formula (pre-reaction as test) of 0.8 glyoxalated.
The whole composition disclosed herein and require and method can be made according to the disclosure and carry out and do not have unsuitable experiment.Although the form that the present invention can be much different is specialized, describe the present invention herein in detail concrete preferred embodiment.The disclosure is the example of the principle of the invention and is not intended to limit the invention to the embodiment of explanation.And any exemplary lists provided herein should be interpreted as the arbitrary combination comprising the project of listing.
Any range provided with constant term or approximate item is intended to comprise all, and any definition used herein is intended to illustrate and unrestricted.Although it is approximate for proposing the large-scale numerical range of the present invention and parameter, the numerical value that specific embodiment proposes be as far as possible accurately report and be understood to include term " about ".But any numerical value comprises inevitable some error by being based upon their standard deviations separately in test experiments and causing inherently.And all scopes disclosed herein are understood to include arbitrarily and all comprise subrange (comprising all marks and integer) wherein.
And, the present invention includes any and all possible combination of some or all of different embodiment described herein.Other reference that any and all patents, patent application, scientific paper and the application quote and any reference quoted herein, all accordingly by quoting whole merging.It is also to be understood that at present various change preferred embodiment described herein or revise apparent to those skilled in the art.This change and amendment can be made and do not deviate from the spirit and scope of the present invention and do not reduce its advantage.Therefore, this change and amendment are intended to be covered by claims.

Claims (13)

1. a composition, described composition comprises: (i) has one or more aldehyde-functionalized polymkeric substance of at least 50,000g/mol weight-average molecular weight, and (ii) at least one stablizer, and wherein said stablizer comprises and being selected from by MgSO 4with its hydrated form, MgCl 2with its hydrated form, magnesium acetate and its hydrated form, ZnSO 4with its hydrated form, Na 2sO 4, NaCl, (NH 4) 2sO 4, and the inorganic salt in the group of the arbitrary combination composition of above component.
2. composition as claimed in claim 1, wherein based on the gross weight of described composition, one or more aldehyde-functionalized polymkeric substance described are with the amount stable existence of 2wt% to 25wt%.
3. composition as claimed in claim 1, one or more aldehyde-functionalized polymkeric substance wherein said comprise by ammonium chloride monomer and acrylamide monomer respectively with 10/90 the multipolymer that formed of weight ratio.
4. composition as claimed in claim 1, the precursor polymer that wherein said aldehyde-functionalized polymkeric substance has aldehyde reaction part by one or more is formed with the molar ratio reaction of 0.05 to 1.5 respectively with one or more simple function types and/or multifunctional type aldehyde.
5. composition as claimed in claim 1, one or more aldehyde-functionalized polymkeric substance wherein said by there is the preformed polymkeric substance of one or more aldehyde reaction parts and one or more be selected from by formaldehyde, paraformaldehyde, oxalic dialdehyde, aldehyde reaction in the group that forms of glutaraldehyde and their combination formed.
6. composition as claimed in claim 5, the aldehyde-functionalized part of at least 2 molar percentages in wherein said aldehyde-functionalized polymkeric substance is at least two reaction.
7. composition as claimed in claim 1, wherein said aldehyde-functionalized polymkeric substance has the weight-average molecular weight of at least 300,000g/mol.
8. composition as claimed in claim 1, wherein based on the gross weight of described composition, the described stablizer in described composition exists with 0.5wt% to 10wt%.
9. one kind for extending the method in the storage time of the composition comprising one or more aldehyde-functionalized polymkeric substance, described method comprises introduces one or more stablizers to one or more aldehyde-functionalized polymkeric substance, wherein relative to comparable non-stabilization aldehyde-functionalized polymer measurement described in the storage time, wherein said stablizer comprises and being selected from by MgSO 4with its hydrated form, MgCl 2with its hydrated form, magnesium acetate and its hydrated form, ZnSO 4with its hydrated form, Na 2sO 4, NaCl, (NH 4) 2sO 4, and the inorganic salt in the group of the arbitrary combination composition of above component.
10. method as claimed in claim 9, one or more the aldehyde-functionalized polymer phases in wherein said composition not demonstrate gel for the aldehyde-functionalized polymkeric substance of comparable non-stabilization during the storage time extended.
11. methods as claimed in claim 9, further comprising the steps: (i) pre-formed polymkeric substance with one or more aldehyde reaction parts, (ii) one or more reactive aldehyde are added with forming reactions mixture to described preformed polymkeric substance, (iii) add one or more stablizers to described reaction mixture, and (iv) causes reaction between described preformed polymkeric substance and one or more reactive aldehyde described to form the aldehyde-functionalized polymer composition of stabilization, or further comprising the steps: (i) pre-formed polymkeric substance with one or more aldehyde reaction parts, (ii) one or more reactive aldehyde described are added to described preformed polymkeric substance, (iii) cause reaction between described preformed polymkeric substance and one or more reactive aldehyde described to form one or more aldehyde-functionalized polymkeric substance described, and (iv) adds one or more stablizers described to form described stable aldehyde-functionalized polymer composition to described aldehyde-functionalized polymkeric substance, or further comprising the steps: (i) pre-formed polymkeric substance with one or more aldehyde reaction parts, (ii) one or more reactive aldehyde is added to described preformed polymkeric substance, (iii) reaction between described preformed polymkeric substance and one or more reactive aldehyde described is caused to form one or more aldehyde-functionalized polymkeric substance, (iv) at any time with arbitrary velocity before above step (i) to (iii), period or afterwards progressively, in batches, semi-batch, add one or more stablizers described continuously or off and on.
12. 1 kinds of manufactures have the method for the medium of cellulosic fibre, and the arbitrfary point place be included in paper technology adds the described composition of claim 1 to medium, described medium has mineral filler alternatively.
13. methods as claimed in claim 12, wherein said composition is added in and is selected from by the green end comprising thin stock and/or thick stock, raises gram moisture eliminator and be indirectly applied on paper by being applied to, be coated directly onto on paper and position in group that the arbitrary combination at above position forms.
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